US4097658A - Process for preparing copolymers of elastomeric properties from olefinic monomers - Google Patents

Process for preparing copolymers of elastomeric properties from olefinic monomers Download PDF

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Publication number
US4097658A
US4097658A US05/714,655 US71465576A US4097658A US 4097658 A US4097658 A US 4097658A US 71465576 A US71465576 A US 71465576A US 4097658 A US4097658 A US 4097658A
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Prior art keywords
butadiene
polymer
mixture
elastomeric properties
copolymer
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Expired - Lifetime
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US05/714,655
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English (en)
Inventor
Artur Simon
Gyula Sarosi
Balazs Keszler
Attila Toth
Maria Rethy
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Muanyagipari Kutato Intezet
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Muanyagipari Kutato Intezet
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/06—Butadiene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/08—Butenes
    • C08F210/10—Isobutene

Definitions

  • the invention relates to a process for preparing copolymers of elastomeric properties by the polymerization of olefinic monomers with catalysts of Ziegler-Natta type mofified by phosgene or by phosgene derivatives, in a medium of hydrocarbons or chlorinated hydrocarbons, followed by the precipitation of the obtained polymer with a C 1-5 alcohol containing an antiageing agent.
  • copolymers having elastomeric properties can be prepared from monoolefins and conjugated diolefins. Further, it is known that an elastomer of this type is the copolymer which can be prepared from propylene and butadiene by means of a Ziegler-Natta catalyst modified by phosgene (British patent specification No. 1,327,664). It is also known that by the polymerization of a mixture of isobutylene and butadiene in the presence of a catalyst of coordinative anionic type, a mixture of polyisobutylene and polybutadiene homopolymers is obtained (J. Polymer Sci. A 9, 3415 /1971/).
  • the aim of the invention is the production of copolymers having elastomeric properties from cheap raw materials, such as the C 4 -fraction formed by the pyrolysis of gasoline.
  • a further aim of the invention is the preparation of a copolymer having an unsaturation of such a degree and such a position that it can be cross-linked by the conventional vulcanisation process, and having further such a molecular weight that the mechanical properties of the cross-linked product correspond to the values of materials used as elastomers.
  • the invention is based on the recognition that the above-specified aims can be attained when the monoolefinic component of the copolymer or the major part of this component carries two methyl side-groups and both methyl groups are linked to the same carbon atom.
  • the crystallization of the copolymer can be avoided better than in the case of many other monoolefine-diolefine copolymers, e.g. of the propylene-butadiene copolymer. Namely, it is generally known that the propylene homopolymer and its copolymers are very inclined to form crystalline structures.
  • copolymers having elastomeric properties can be prepared from butadiene and isobutylene and/or n-butanes and optionally from saturated hydrocarbons by using suitable proportions of the components and using the in itself known catalyst system of phosgene-aluminium alkyl-TiCl 4 .
  • the invention is based on the recognition that the polymerization of olefinic monomers can be carried out even in the presence of saturated hydrocarbons, and thus also the C 4 -fraction obtained by the pyrolysis of gasoline can be used as a starting material of polymerization.
  • the invention is a process for preparing copolymers of elastomeric properties by the polymerization of olefinic monomers with catalysts of Ziegler-Natta type modified by phosgene or phosgene derivatives, in a medium of hydrocarbons or chlorinated hydrocarbons, followed by the precipitation of the obtained polymer with a C 1-5 alcohol containing an antiageing agent, characterized in that a mixture of isobutylene and butadiene containing from 30 to 95 % of butadiene is used as olefinic monomer, the said mixture containing, if desired, at most 20 % by weight of butene-1 and/or butene-2, related to the total amount of monomers.
  • the catalyst can be decomposed, prior to precipitating the polymer, by the addition of 5-25 ml, preferably 15 to 20 ml of a C 1-5 alcohol, preferably methanol, related to 1 g of TiCl 4 present in the applied catalyst, the added alcohol containing an antiageing agent.
  • a filler preferably carbon black or aerosil, related to the polymer, can be added to the solution of the polymer.
  • the C 4 -fraction obtained by the pyrolysis of gasoline and containing at least 30 % of butadiene is used as olefinic monomer.
  • the polymer In an unloaded state the polymer consists of molecules of a completely amorphous structure though of a linear type, and these molecules have, when vulcanized and stretched, a rubber-like arrangement.
  • the copolymer can be vulcanized in a way conventional in the rubber industry, e.g. by means of sulphur.
  • the vessel is thermostated at 40° C under continuous stirring for 4 hours, then the residual monomers are blown off, and the polymer is precipitated from the solution by adding methanol of a 15-fold volume, referred to the reaction mixture, and containing 0.1 g of phenyl- ⁇ -naphthylamine.
  • the precipitated polymer is separated from the mother liquor, then washed with methanol and dried in vacuo at 40° C.
  • the amount of the obtained polymer is 10 g; its intrinsic viscosity measured in toluene at 30° C is 1 and its degree of unsaturation determined according to Wijs amounts to 390 g I 2 /100 g of polymer.
  • Example 2 One proceeds as described in Example 1, with the difference that 30 g of a monomer mixture composed of 12 g of butadiene, 8 g of isobutylene, 5 g of butene-1 and 5 g of butene-2 is used, and instead of trichloroethylene an identical volume of tetrachloroethylene is applied.
  • the amount of the obtained polymer is 8.5 g; its intrinsic viscosity measured in toluene at 30° C is 0.79, and its degree of unsaturation determined according to Wijs is 340 g I 2 /100 g of polymer.
  • the amount of the obtained polymer is 7.9 g, its intrinsic viscosity measured in toluene at 30° C is 0.8 and its degree of unsaturation determined according to Wijs is 330 g I 2 /100 g of polymer.
  • Example 3 One proceeds as described in Example 3, with the difference that instead of a phosgene solution 0.44 ml of a 1 M solution of acetyl chloride in trichloroethylene is applied.
  • the amount of the obtained polymer is 5.0 g; its limit viscosity measured in toluene at 30° C is 0.48, and its degree of unsaturation determined according to Wijs amounts to 361 g of I 2 /100 g of polymer.
  • Example 3 One proceeds as described in Example 3, with the difference that instead of trichloroethylene an identical volume of toluene is applied.
  • the amount of the obtained polymer is 6.5 g; its intrinsic viscosity measured in toluene at 30° C is 0.58, and its degree of unsaturation determined according to Wijs is 360 g I 2 /100 g of polymer.
  • the mixture is put into a press for 40 minutes at 160° C.
  • the characteristics of the rubber prepared in this way are as follows:
  • Example 2 One proceeds in the way as described in Example 1, with the difference that prior to precipitation with methanol the polymer solution is treated with 2 ml of methanol containing 0.1 g of phenyl- ⁇ -naphthylamine, in order to decompose the catalyst. Subsequently, the precipitated residues of the catalyst are removed by filtration, then 50 per cent by weight of carbon black (related to the amount of polymer) is mixed up with the polymer solution. Then the copolymer is precipitated by adding, under stirring, methanol of a 15-fold volume, related to the mixture comprising the solvent, and containing an antiageing agent.
  • the precipitated copolymer is separated from the mother liquor, washed with methanol and dried in vacuo at 40° C.
  • the dried substance is slightly sticky and can be readily processed further e.g. by working up to a mixture of the following composition in a roll mill at 20° C:
  • the above mixture is then put into a press for 40 minutes at 143° C.
  • the rubber prepared in this way has the following characteristics:

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US05/714,655 1975-08-19 1976-08-16 Process for preparing copolymers of elastomeric properties from olefinic monomers Expired - Lifetime US4097658A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
HU75MU00000542A HU172849B (hu) 1975-08-19 1975-08-19 Sposob poluchenija ehlastomernogo kopolimera iz izobutilena i butadiena
HUMU542 1975-08-19

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US4097658A true US4097658A (en) 1978-06-27

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US (1) US4097658A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
JP (1) JPS5235287A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
BE (1) BE845297A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
CS (1) CS190731B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DD (1) DD125412A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE2636930A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
FR (1) FR2321510A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
GB (1) GB1504236A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
HU (1) HU172849B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
IT (1) IT1076933B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
NL (1) NL7609116A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
SU (1) SU828973A3 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1359189A1 (en) * 2002-04-26 2003-11-05 Bayer Inc. Rubber composition for tire treads

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4572496A (en) * 1983-09-08 1986-02-25 Moore Business Forms, Inc. Trim rewinder with automatic stop
DE19718201A1 (de) * 1997-04-30 1998-11-05 Bayer Ag Neue Terpolymere aus Isoolefinen, konjugierten Diolefinen und ein- oder mehrfach ungesättigten organischen Verbindungen

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1327664A (en) 1970-05-14 1973-08-22 Bridgestone Tire Co Ltd Method for manufacturing butadiene-propylene copolymers
US3808177A (en) * 1971-06-08 1974-04-30 Exxon Research Engineering Co High molecular weight,high unsaturation c4-c10 isoolefin conjugated diene copolymers
US3850897A (en) * 1971-11-26 1974-11-26 Snam Progetti Procedure for the production of polymers and copolymers of isobutylene

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1327664A (en) 1970-05-14 1973-08-22 Bridgestone Tire Co Ltd Method for manufacturing butadiene-propylene copolymers
US3808177A (en) * 1971-06-08 1974-04-30 Exxon Research Engineering Co High molecular weight,high unsaturation c4-c10 isoolefin conjugated diene copolymers
US3850897A (en) * 1971-11-26 1974-11-26 Snam Progetti Procedure for the production of polymers and copolymers of isobutylene

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1359189A1 (en) * 2002-04-26 2003-11-05 Bayer Inc. Rubber composition for tire treads
US20030220437A1 (en) * 2002-04-26 2003-11-27 William Hopkins Rubber composition for tire treads

Also Published As

Publication number Publication date
NL7609116A (nl) 1977-02-22
DD125412A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1977-04-20
SU828973A3 (ru) 1981-05-07
FR2321510B3 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1979-05-11
GB1504236A (en) 1978-03-15
IT1076933B (it) 1985-04-27
DE2636930A1 (de) 1977-03-03
JPS5235287A (en) 1977-03-17
HU172849B (hu) 1978-12-28
CS190731B1 (en) 1979-06-29
BE845297A (fr) 1976-12-16
FR2321510A1 (fr) 1977-03-18

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